CN103501596B - For improving compositions and the method for the physical stability of agricultural Oil-based Suspension preparation - Google Patents
For improving compositions and the method for the physical stability of agricultural Oil-based Suspension preparation Download PDFInfo
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- CN103501596B CN103501596B CN201280020206.XA CN201280020206A CN103501596B CN 103501596 B CN103501596 B CN 103501596B CN 201280020206 A CN201280020206 A CN 201280020206A CN 103501596 B CN103501596 B CN 103501596B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing >N—S—C≡(Hal)3 groups
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
Abstract
Comprising the active component and at least one unsaturated rubber type copolymer or the agriculture Oil-based Suspension preparation of its mixture being suspended in finely divided form in oil, wherein this rubber-type copolymer comprises at least styrene as residue.
Description
Invention field
The present invention relates to the stabilisation of the Oil-based Suspension preparation of the subdivided solids of agricultural active.The present invention relates more specifically to bag
Oil-based Suspension preparation containing the agricultural active solid of the stability with improvement.
Background of invention
Comprise and be suspended in the preparation as the agricultural active solid in the oil of the key component of continuous phase and have been observed that favorably
Process in agricultural substrate.The example of this type of preparation is referred to as OD(" oil dispersible preparation " by CropLife International) and
OF(" can oil miscible flowable concentrate (oil-miscible flowable concentrate) ") preparation.
This type of preparation provides some advantage for end user.They can prepare active component with solid suspended form, due to
Hydrolytic instability, these compositions can not be prepared in water.This type of preparation allow also to mix oil base adjuvant in said preparation with
Strengthen effect.Additionally, in many cases, active component has dissolubility to limit to being loaded into the preparation such as measurer in cream preparation
System, is therefore suspended in oil based system and may produce the preparation that activity component concentration is higher than the most possible concentration.
It is to need physically stable between possible long pot life to oil base agricultural formulations, the such as major limitation of OD and OF preparation
Said preparation, to be at being always available for the form of final use subsequently.Generally, OD or OF preparation can be in time through table
Reveal active ingredients particles and settle into the most redispersible strong layer, or particle precipitation is in the lower floor of fluid column, so that there is phase
Separate.This is commonly referred " syneresis ".Density according to active component and the density of oil phase used, it is also possible to find to live
Property component particle moves in the top layer of fluid column.This is described generally as " reversely " or " top " syneresis.Despite the presence of purport
At the oil-based surfactant dispersant preventing divided particles from flocculating, but still such physical instability can occur.
In order to make stabilizer can be used in oil base agricultural suspension, it must be at the wide temperature range of usual 0 DEG C to 54 DEG C
Interior offer long term physical stability, still keeps being low enough to be actually used in manufacture preparation and for its final use subsequently simultaneously
Viscosity.Required typical viscosities is less than 2,000 centipoise (" cP "), preferably smaller than 1200cP.
The various antihunt means of oil-based formulation are known.The typical stabilizer being currently used for oil-based formulation includes organic changing
The HECTABRITE DP of property, as available from Elementis SpecialtiesSeries.Being permitted of having tested
In many body system, it has been found by the present inventors that these stabilizers seem and not always provide to accelerate storage under acceptable viscosity
Stability in temperature required scope when depositing.Additionally, the thickening agent used in certain situation seems to suppress used some
Common non-aqueous dispersion agent.
This area currently also uses the silicon dioxide of hydrophobically modified.But, being limited in of this type of stabilizer, required thin
Water degree not can be according to oil used fully regulation.Additionally, such stabilizer usually requires that a small amount of hydrophilizing agent of use, as
Water, to help forming thickening structure in oil phase.Water and silicon dioxide are used together and hinder said preparation anhydrous in many cases
To avoid the purpose of active component chemical degradation.In many cases, the silica stabilizer needed for undesirable sedimentation is prevented
Amount also produce high viscous and unpractical preparation.
Additionally, the stabilisation that some active component is under their desired concentration has difficulties.Accordingly, it would be desirable to for oil
The stabilizer of the improvement of base agricultural suspension formulation.
Use the unsaturated rubber type copolymer of synthesis, such as SB and styrene-polyethylene/poly-
Propylene is known as binding agent and the thickening agent of coating or rheology modifier.But, with regard to applicant knowledge in one's power, this type of
Agricultural Oil-based Suspension preparation not yet it is actually used in before polymer.This is possibly due to when this base polymer (example in a conventional manner
As by adding solid after being dispersed through and grinding active component under high shear) not yet obtain when adding in oil-based suspension
Obtain gratifying result.
The present invention attempts to provide the stable oil base agricultural suspending agent improved and manufacture method thereof.More particularly, present invention examination
Figure reduces or improves the shortcoming and problem found in prior art as far as possible.
Summary of the invention
It has now unexpectedly been found that, based on including but not limited to styrene and butadiene；Styrene, ethylene and propylene；
It is being formulated into premix group according to method described herein with the unsaturated rubber type copolymer of styrene and the monomer of isoprene
Can be oil base agricultural formulations time in compound, as OD or OF preparation provides the physical stability greatly improved.
According to an aspect of the present invention, it is provided that agricultural Oil-based Suspension preparation, it comprises: be suspended in finely divided form in oil
Active component；With at least one rubber-type copolymer or its mixture, wherein said rubber-type copolymer comprises at least benzene second
Alkene is as residue.It is highly preferred that this copolymer be selected from SB, styrene-polyethylene/polypropylene or
Styrene-isoprene copolymer containing cinnamic polymer.This analog copolymer can be random, alternately or block form or
Its mixture.
Additional list can be comprised not change the content of this copolymer integral form in oil solution or dispersion
Body.In its most preferred form, said preparation comprise further selected from butadiene, ethylene, propylene, isoprene or butylene or its mix
Another olefin hydrocarbon molecules of compound.This type of monomer can include alpha-olefin and vinyl olefins.The example of this base polymer includes obtaining
From Kraton Polymers'sSeries of polymers.Most preferablyG based polymer, asG-1701 polymer.
It is suitable for inclusion in the active component in OD preparation preferably containing at least a kind of antifungal, Insecticides (tech) & Herbicides (tech), plants
Thing growth regulator, acaricide, nematicide, molluscicide, algicide or other pesticide or its mixture.More particularly, activity
Composition is selected from, but is not limited to, antifungal, as alkylidene is double (dithiocarbamate), such as Mancozeb (i.e. ethylenebis
Dithiocarbamate and the complex of Mg and Zn)；Zineb (i.e. (ethylenebis aminodithioformic acid) zinc complex)
Or ziram (the most double (dimethyl dithiocarbamic acid) zinc)；Phosethyl-Al (i.e. three O-ethylphosphonic acid aluminum)；Tebuconazole is (i.e.
(RS)-1-(4-chlorphenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-yl methyl)-amyl-3-alcohol)；Copper hydrate；With
COPPER OXYCHLORIDE 37,5；Phthalimide, such as captan, (i.e. N-(trichloromethylthio)-hexamethylene-4-alkene-1,2-bis-formyl is sub-
Amine)；Herbicide, such as sulfonylureas, such as nicosulfuron (i.e. 2-[(4,6-dimethoxypyridin-2-base carbamoyl) sulfonamides
Base]-N, N-dimethyl nicotinamide)；With azimsulfuron (i.e. l-(4,6-dimethoxypyridin-2-base)-3-[1-methyl-4-
(2-methyl-2H-tetrazolium-5-base) pyrazoles-5-base sulphonyl] urea)；Triazolo pyrimidine, such as Flumetsulam, (i.e. 2', 6'-bis-is fluoro-
5-methyl [l, 2,4] triazol [1,5-α] pyrimidine-2-sulfonanilide)；With penoxsuam (i.e. 2-(2,2-(difluoro ethoxy
Base)-N-(5,8-dimethoxy [1,2,4] triazol [1,5-c] pyrimidine-2-base)-6-(trifluoromethyl) benzsulfamide)；Triazine,
Such as G-30027 (i.e. 6-chloro-N-ethyl-N'-(1-Methylethyl)-1,3,5 ,-triazine-2,4-diamidogen)；Phenylurea herbicide,
Such as diuron (i.e. 3-(3,4-Dichlorobenzene base)-1,1-dimethyl urea)；Insecticide, such as Aldicarb (i.e. 2-methyl-2-(methyl sulfur
Generation) propionic aldehyde-O-methylcarbamoyl oxime)；Carbaryl (i.e. methyl carbamic acid 1-naphthalene ester)；With diflubenzuron (i.e. N-[[(4-chlorobenzene
Base)-amino] carbonyl]-2,6-difluorobenzamide).
It has been found by the present inventors that above-mentioned preparation used in anti-settling and physical stabilization system adds have
C8-C20Some of hydrocarbyl portion long hydrocarbon chain organic acid or its salt produce specific advantages.Therefore, the preparation of the present invention can wrap further
Containing at least one long hydrocarbon chain organic acid or hydrochlorate.
Acylate is preferably selected from the salt of fatty acid；Substituted or unsubstituted straight or branched alkyl or the salt of alkenyl；
With replacement or the salt of unsubstituting aromatic yl.
If this acylate comprises soap, this fatty acid is preferably selected from C8-C18Fatty acid, as oleic acid, stearic acid,
Myristic acid, Palmic acid, lauric acid and multi-hydroxy stearic acid.Salt-forming cation selected from sodium, calcium, magnesium, potassium, aluminum, ammonium, alkylammonium or
Alkanol ammonium and other common monovalence, bivalence and trivalent ion.This soap is more preferably selected from enuatrol, potassium oleate, hard
Fat acid sodium, two calcium oleates, distearyl acid calcium and multi-hydroxy stearic acid calcium.
If this acylate comprises the salt of alkyl, hydrocarbyl portion is preferably selected from C10-C18Carbochain.This alkyl is the most not
Substituted straight chained alkyl.The salt forming anion of this organic acid is preferably selected from sulfate radical, sulfonate radical, phosphate radical or phosphonium acid ion；
And salt-forming cation be preferably selected from sodium, calcium, magnesium, potassium, aluminum, ammonium, alkylammonium or alkanol ammonium and other common monovalence, bivalence and
Trivalent ion.In a preferred embodiment, this acylate is sodium lauryl sulphate.
If this acylate comprises the salt of alkenyl, hydrocarbyl portion is preferably selected from C12-C16Carbochain.This alkenyl is preferred
It it is unsubstituted straight alkenyl.The salt forming anion of this organic acid is preferably selected from sulfate radical, sulfonate radical, phosphate radical or phosphonate radical
Ion.The salt forming anion of this organic acid most preferably sulfonate ion.Salt-forming cation be preferably selected from sodium, calcium, magnesium, potassium, aluminum,
Ammonium, alkylammonium or alkanol ammonium and other common monovalence, bivalence and trivalent ion.In another preferred embodiment of the present, comprise
The organic salt of alkenyl is alkene sulfonic acid sodium salt blend (sodium salt of an olefin sulphonate
Blend).
If this acylate comprises the salt of aryl, in a preferred form, this aryl is preferably alkylaryl, wherein
Alkyl chain is preferably selected from C10-C16Carbochain.This alkyl chain is more preferably straight chain.The salt forming anion of this organic acid is preferably selected from sulfur
Acid group, sulfonate radical, phosphate radical or phosphonium acid ion.In further preferred embodiment, comprise the acylate of alkylaryl
It it is linear alkylbenzene sulfonate (LAS).
Before normally sowing OD preparation by foliar spray, it is diluted in water, therefore it is required that there is surfactant breast
Agent.But, in the case of OF preparation, owing to said preparation is designed to dilute further in oil, it is not necessary to surfactant
Emulsifying agent.Said preparation is similar to OD preparation in other side.OD formulation requirements active component is present in oil with state in small, broken bits.Suitable
Oil phase for OD and OF preparation includes being not enough in the degree causing crystal growth or physical instability dissolve active component
Any liquid at ambient temperature.
The oil being typically found in anti-settling and physical stabilization system can include, but not limited to paraffin oil, such as kerosene,
Such as available from Exxon Chemical'sOne of D series, more preferablyD130；Available from
Caltex's12；With available from Total'sG250H.Seed grease, such as methyl oleate and
Ethyl ester, methyl soyate and ethyl ester and their corresponding fatty acid are the most suitable.Aromatic hydrocarbons, such as alkylbenzene and alkylnaphthalene, poly-alkane
Support glycol ethers, fatty acid diesters, fatty alkyl amide and diamides, carbonic acid two alkylene ester, ketone and alcohol are the most suitable.
The suspension formulation of the present invention can comprise other additive, lives as active component is suspended in oil the surface of rear addition
Property agent emulsifying agent is to pass this oil phase so that emulsifying form is defeated；Surfactant-dispersed agent and physics in addition to those of the present invention are steady
Determining agent, they may act as anti-settling or anti-dehydrating contracting agent.When it is present, can be steady with the colloid of the solid phase after up to grinding
Any suitable amount of the level needed for fixedization comprises this surfactant-dispersed agent.
The surfactant-dispersed agent being applicable to OD and OF preparation is preferably selected from, but is not limited to, fatty acid-ployalkylene glycol
Condensation substance, as2510 dispersants；Polyamine-fatty acid condensates, as4890 dispersions
Agent；Random polyester condensation thing, as2520 dispersants；With the salt of polyolefin condensation substance, as2422 dispersants, they are all the products of Huntsman Corporation.
The selection of the emulsifying agent of OD preparation is often depending on the type of oil used.Generally, there is low hydrophobic-thin fat balance
The surfactant of (" HLB ") is suitable.HLB needed for the most of oil phases used in OD or OF preparation is usually less than 10.
Such surfactant is preferably selected from, but is not limited to, one or more ethoxylized fatty alcohols, sorbitan ester and they
Corresponding ethoxylate, ethoxylated fatty acid, ethoxylated castor oil, the calcium of alkyl benzene sulphonate and ammonium and alkylammonium
Salt, salts of alkyl sulfosuccinates salt, ethylene oxide-propylene oxide block copolymer, ethoxylated alkylamine and ethoxylated alkyl
Phenol.
Comprise Mancozeb and be selected from castor oil ethoxylate, especially as the emulsifying agent of the OD preparation of active component
It is3512 emulsifying agents, alcohol ethoxylate, particularly12A3,12A4 and 17A2 fatty acid ethoxy
Compound, asOF6, sorbitan ester ethoxylate, asT85, sulfosuccinate, as3665 emulsifying agents, the amine of DBSA and calcium salt, asEVM series of products, these all may be used
Available from Huntsman Corporation.
Additional emulsifiers can be added on demand to keep internal structure and the viscosity of said preparation.In such cases, originally
The preparation of invention more preferably comprises the emulsifying agent with the HLB higher than the common HLB of oil-continuous phase.Although involved by uncertain really
Cut mechanism, but it is believed by the inventors that more hydrophilic molecule be added with the internal structure restructuring helping said preparation.
Additive reagent is more preferably selected from one or more alkyl alkoxylates or the double block of ethylene oxide/propylene oxide is total to
The ethylene oxide/propylene oxide list block copolymer that polymers or alkyl cause, their HLB exceedes the required HLB of oil-continuous phase.
These reagent more preferably have HLB, the HLB of most preferably from about 13 higher than about 10.
This alkyl alkoxylates is preferably selected from alcohol ethoxylate, and wherein this ethoxylate is most preferably based on comprising
C10-C18The fatty alcohol of chain and the molal quantity of oxirane that wherein adds are more than 20.In a preferred embodiment, this alkane
Epoxide compound is available from Huntsman CorporationKM20 surfactant.
Most preferably ethylene oxide/propylene oxide block copolymer be HLB be higher than about 10 and molecular weight more than 2500amu
That, be selected fromPE75、The list that the diblock copolymer of PE103 and butyl alkyl cause is embedding
Section copolymer, as5429, these are all available from Huntsman Corporation.
Other additive that can add in said preparation includes coloring agent, such as pigment and dyestuff；Cosurfactant；pH
Regulator and other chemical stabilizer；Defoamer；Essence；Odor mask；With other Auto-regulating System of Density of Heavy Medium solvent.Said preparation also can comprise peace
Full agent.
The scope of the present invention also extends to comprise unsaturated rubber type copolymer, oil and/or arsol and the most organic
Acid or acylate and/or be suitable for prevent the premix composition of the dispersant of the flocculation of Oil-based Suspension preparation and agglomeration.
Rubber-type copolymer in this premix composition preferably exists with 4-20%w/w, if using arsol, with 10-
85%w/w, most preferably exists with 10-50%w/w.It is pre-that oil or solvent or a combination thereof are preferably present in this with the 80-95% of total composition
In mixing composition.If it does, acylate in premix composition preferably with the 0-15%w/w of total composition, more preferably with always
The 10-15%w/w of compositions exists.In this premix composition, the amount of surfactant-dispersed agent is generally with the 0-5% of total composition
W/w, preferably 2.0-3.0% exist.
Another further aspect, the method that the scope of the present invention extends to be prepared Oil-based Suspension preparation by initial premix composition.Should
Premix composition is preferably as follows manufacture: by usual 70-100 DEG C, heat, by the present invention's under the high temperature of preferably 80-90 DEG C
Unsaturated rubber type copolymer is dissolved in oil to produce without gel and the limpid homogeneous liquid of undissolved solid.Generally have only to
Effectively stirring can be achieved with this point.Then adding organic acid or its salt in this oil solution, it is dispersed or dissolved in this substantially
In solution.Then the mixture of copolymer, organic acid or its salt and oil is preferably cooled to 60 DEG C, hereafter by a certain amount of dispersant
It is substantially dissolved in this premix composition.Then this premix composition is cooled to ambient temperature storage in case using after a while.
Or, preferably after reaching 60 DEG C or lower temperature, solid phase (active component) is added in this premix composition.
In another preferred aspect, the present invention relates to prepare oil base agrochemical suspension formulation, such as the method for OD or OF preparation, bag
Include preferably according to the method for the invention described above prepare premix composition, the most not with or with oily and the most other other dispersion
Active component is dispersed substantially throughout the step in this premix composition by agent together.Due to this premix composition generally with about 10%
Concentration is with in the final formulation, and this rubber-type copolymer is preferably with 0.05-2%w/w, and most preferably 1.0-2.0%w/w is present in finally
In preparation.Similarly, if it does, this organic acid or its salt are the most preferably with the 0-1.5%w/w of total composition, more
Preferably exist with the 0.4-1.0%w/w of total composition.In final preparation, the amount of surfactant-dispersed agent is generally with total composition
0-10%w/w, preferably 2.0-5%w/w exist.The surplus of final OD/OF preparation comprises oil ingredient.
Generally in high shear mixing (as passed throughBlender obtain) under active component is dispersed in premix
In compositions, then high shearing condition (as at ball mill, asIn KDL obtain) under grind.Generally need
Grind to be down to the granularity of active component be suitable for preventing from settling within a few hours and such as providing suitable effect when applying
Scope.This desired particle size usual receptor 1 activity composition and the respective Effects of Density of oil phase；However, it may generally be desirable to 1-10 micron,
The particle mean size of preferably 1-3 micron.
Invention as herein described is the method preparing the OD preparation comprising active component in another further aspect, including step:
A) premix composition is prepared according to said method；
B) not with or together with oily and the most other other dispersant, active component is dispersed in this premix composition
In；
C) active component dispersion is ground to realize the particle mean size of 1-12 micron；
D) it is optionally added to a kind of other organic acid or its salt；
E) surfactant emulsifiers is added；With
F) optionally through the additional oily final content of active component that regulates to realize continuous phase,
Wherein step a) is to e) carrying out in any order.
In a particularly preferred embodiment of the present invention, this active component comprises Mancozeb, is preferably greater than
The concentration of 400g/L.In another preferred form, said preparation comprises the Mancozeb more than 580g/L concentration.The present inventor is favourable
Ground can manufacture the preparation comprising the Mancozeb more than 480g/L concentration, it has been found that said preparation is steady in a long-term, does not has viscosity
Ill effect.In this preparation, do not observe hard layer, and when said preparation stores more than 6 weeks at 54 DEG C still for fluid/
Dumpable.Present invention provide an advantage in that it obtains the excellent of Mancozeb and stablizes high carrying capacity suspension formulation, and other
Antisettling agent, as modified HECTABRITE DP seems invalid wherein.
It has been found by the present inventors that by use polymer stabilizer premix composition in oil (its may be constructed or
Do not constitute the major part of disperse medium), the stability being greatly improved can be realized in tested OD and the OF preparation of difficulty.One
Denier is configured to, OD or the OF preparation made by the method for the present invention estimates that stable storing is most at a temperature of-5 DEG C to 54 DEG C
2 weeks, and stablize most 2 years at ambient temperature.
Detailed Description Of The Invention
Description below only relates to specific embodiments of the present invention and is not intended to scope of the invention is limited to these
Specific embodiments.Especially, description below is illustrative and not restrictive.Variation and amendment to disclosed method are
It will be obvious to a person skilled in the art that they are not necessarily depart from the essence of the present invention.
Describe referring now primarily to the respective high carrying capacity suspension formulation of Mancozeb, diuron, G-30027 and captan
The present invention.The anticipated suspension formulation to other solid active agent insoluble in this continuous phase in oil can find similar results.
Typical OD preparation has the composition described in table 1 below.
Typical component needed for table 1. oil dispersion preparation
| Component | Typical amount, %w/w | Purposes |
| Active component | <60 | As poison |
| Dispersant (oil-soluble) | 3-8 | Prevent particle accumulation |
| Emulsifying agent | 5-20 | The emulsifying oil phase when preparation is added in water |
| Antisettling agent and structural agent | 0.5-5 | Prevent sedimentation and syneresis |
| Oil | Surplus | Form continuous phase |
Embodiment
Research on The Rheology
Without active component, the combination manufacturing oil and rubber-type copolymer adds acylate to check in this system,
Including soap, sulfate and sulfonate；High HLB nonionic surfactant；Dispersant and the effect of emulsifying agent.This be
The preparation subsequently of demonstration provides model.
Flowing and vibration measurement:
The AR2000ex flow graph from TA instruments is used to measure.
Flow program:
Cone geometry 4cm2 °, gap 51 μm or slab geomitry 4cm, gap 150 μm；Temperature 20 DEG C；Shear rate 0s-1To 100s-1, peak is maintained at 100s-1And speed is from 100s-1It is down to 0s-1。
Temperature scanning:
Cone geometry 4cm2 °, gap 51 μm or slab geomitry 4cm, gap 150 μm；Strain with the regulation % in LVR and the frequency of 1Hz
Rate is from 5 DEG C to 55 DEG C temperature scannings.
Embodiment 1 to 4 investigates dispersant and the emulsifying agent effect to the rubber-type copolymer in oil.
Embodiment 1
The preparation of rubber-type copolymer base material
To 88 parts of w/w4 parts are added in 12G1701.Gained blend is stirring at 70 DEG C
Mix several hours of lower heating until forming gel.The gel formed is hereinafter referred to asBase material.
Embodiment 2
To 90%w/w from embodiment 1 under 40 DEG C of heatingG1701 base material adds 10%w/w2510 until the latter is dissolved.
Embodiment 3
To the embodiment 1 of 90%w/wG1701 base material adds 10%T85(is dehydrated
Sorbitol trioleate ethoxylate) andKBE3(alcohol ethoxylate) 1:1 blend.This common
That mixes thing quotes entitled EDSA08/09.These are for emulsifyingThe typical oil-water emulsifiers of 12 oil.
Embodiment 4
To the embodiment 1 of 90%w/wG1701 base material adds 10%w/w's3665(exists
Dialkyl sulfosuccinate in arsol)；For emulsifyingAnother typical emulsifiers of 12 type oil.
The flow curve of embodiment 1 to 4 shows in FIG.
G1701 polymer is being present in alone according to embodiment 1Abundance is provided time in 12 oil
Yield strength and apply in temperature range flexible.This shows that it is suitable as the structural agent of OF preparation.
Add according to embodiment 22510 dispersants strengthen yield strength, but this system is more than room temperature
Lose it elastic.This shows2510 at room temperature provide desirable viscosity, but in the required storage of OD preparation
Good stabilisation is not provided under the higher temperature of condition.
Typical emulsifiers is used to show poor elasticity and therefore stability below room temperature according to embodiment 3, but along with
Temperature improves, it appears that show improvement.This shows that, in the case of there is rubber-type copolymer, these emulsifying agents cause relatively low
At a temperature of less than optimal structuring effect.
Use according to embodiment 43665 show to destroy the yield value during flowing experiment and in whole temperature
Elasticity in the range of degree.Interpolation interference yield strength (flowing) of this emulsifying agent and elasticity at a lower temperature.This shows3665 structures suppressing this rubber-type copolymer in the case of there is not other additive.
Embodiment 5 to 8 display existsBase material adds the effect of other dispersant.
Embodiment 5
To 90%w/w from embodiment 1 under 40 DEG C of heatingBase material adds 10%w/w polyhydroxy stearic
Acid is until it dissolves.
Embodiment 6
To 90%w/w from embodiment 1 under 40 DEG C of heatingBase material adds 10%w/w Polyethylene Glycol
MW1500 (PEG1500) is until uniformly.
Embodiment 7
To 90%w/w from embodiment 1Base material adds 10%w/w4890(gathers
Amine-fatty acid condensates) and stir until it dissolves.
Embodiment 8
To 90%w/w from embodiment 1Base material adds 10%w/w2422(polyene
Hydrocarbon condensation substance salt) and stir until it dissolves.
The flow curve that embodiment 5 to 8 compares with embodiment 1 and 2 shows in fig. 2.
Multi-hydroxy stearic acid according to embodiment 5, according to embodiment 74890 and according to embodiment 8
'sStructural table is revealed illeffects by the interpolation of 2422.The interpolation performance of the PEG1500 according to embodiment 7
Go out certain beneficial effect.
These embodiments show2510 be in the case of there is not other additive any with rubber
The optimum dispersant that type copolymer is used together.
The soap effect to rubber-type copolymer
Embodiment 9 to 16 display existsThe various soaps being combined with rubber-type copolymer in oil
Effect (note:Oil is C12-C18Hydrocarbon ils.It is used with embodiment before12 compare
There is relatively low carbon distribution).Embodiment 9 is hereinafter referred to asBase material.
To preparing rubber-type copolymer pre-composition as described in embodiment 1 and 2.By using top set agitator or optionally leading to
Cross high shear mixing and simply disperse this salt, mix soap.
Compositions used in embodiment 9 to 16
The flow curve of embodiment 9 to 16 shows in figs. 3 and 4.
Fig. 3 show toBase material adds the effect of soap.At all situations
Under, it is achieved the favorable elasticity in temperature required scope, effect is better than base material when being used alone.
Fig. 4 showsIn the presence of 2510 dispersants toBase material
The effect of middle addition soap.It can be seen that this soap compensates2510 bullets at relatively high temperatures
Property loss, wherein enuatrol and calcium stearate behave oneself best.
Sulfate and the sulfonate effect to rubber-type copolymer
Embodiment 17 and 18 display toBase material adds sulfate and the work of sulfonate
With.LZ/B is sodium lauryl sulphate salt surfactant.1004 is alkene sulfonic acid salt blend
Thing sodium salt surface active agent.Embodiment is prepared in the way of to the description of embodiment 9-16.
The flow curve of embodiment 17 and 18 shows in Figure 5, as comparing display embodiment 9,10 and 12.
The interpolation of LZ/B is of value to holding similarly and containsThe structuring of 2510 is altogether
The elasticity of mixed thing.1004 also partly overcome use2510 elasticity at high temperature run into
Loss.
Conclusion is that alkyl sulfate and alkylsulfonate are promoting aspect of performance and the fat of rubber-type copolymer further
Hydrochlorate behaves like.
To
Base material adds the effect of higher HLB alcohol ethoxylate
WithG250H carries out this research.From embodiment 9
Base material is being measured before rheological characteristic with 10%G250H and 5%TERSPERSE2510 dilutes.
KM series is C16-C18Alcohol ethoxylate.Numerical value after KM refers to that existing oxirane rubs
That number.
Embodiment 19 to 23 display existsIn the presence of 2510 dispersants to
Base material adds the effect of alcohol ethoxylate.
The flow curve of embodiment 19 to 23 shows in figure 6.
From fig. 6 it can be seen that the interpolation of alcohol ethoxylate expands similarly2510The notable temperature losing its elasticity in base material.Ethoxylation scope to 20 to 50 finds
Optimum.80 mole ethoxylates are likely to too insoluble in oil phase, and this may be lower than the reason of optimum performance.
This shows to add HLB more than 10(i.e. more than the value needed for this oil of emulsifying) the beneficial effect of alcohol ethoxylate,
HLB higher than 13 shows the best use of.
Example of formulations
UseG-1701 prepares a series of embodiment OD preparation and uses three kinds of agricultural active to become to measure
Divide the function theomorphism giving basic model preparation.G-1701 as use arsol precast gel,
As using the precast gel of paraffin oil or being used in combination with various acylates.
Unless otherwise specified, all formulations is imposed the accelerating storage at 54 DEG C, if it is possible, basis before storage
CIPAC MT161 carries out suspendability measurement with 2%w/v in 20ppm Environmental Water.Although this class testing Bu Shi food and agricultural organization
(" FAO ") official demands to OD preparation, but in this case, after mensuration residue suspendability is to characterize dilution best
The quality of oil/solid dispersion.
Embodiment 24(contrast)
CompriseThe preparation of the OD preparation of antisettling agent
Prepare said preparation as follows:
Manufacture preparation the most as follows: by oil dispersant2510 points
Powder is dissolved in 90% oil phase and is added to by Mancozeb (85%w/w technology) powder under high shear mixing wherein to be formed
Slurry, it uses ball mill grinding to manufacture particle mean size (d subsequently0.5) less than the abrasive of 5 microns (μm).The most under agitation
Add in this abrasive other surfactant andThickening agent.
Said preparation is stored at 54 DEG C.Although the emulsifying of this preparation is satisfactory, but after less than 5 days, said preparation
Form thick gel, there is the most redispersible strong settled layer.
This preparation shows, the most a large amount ofThickening agent can not prevent sedimentation and be this product
Gratifying viscosity is provided.
The preparation of the OD preparation of non-structure agent
Embodiment 25(contrast)
Prepare said preparation as follows:
By under shear-mixed, diuron activating agent is added to oil andWith system in 2510 dispersants
Make 58%w/w pre-composition, prepare preparation.Then this pre-composition is ground to the particle mean size less than 2 microns to produce grinding
Material.Add in this abrasive under high shear mixing (7000rpm, 2 minutes)3665 emulsifying agents, then enter one
Step addsG250H to join full volume, then further high shear mixing until uniformly.
Said preparation is stored at 54 DEG C and 20 DEG C, observes the hard layer of thickness after 7 days.Said preparation also shows 53%
Syneresis.
Embodiment 26(contrast)
Use the OD preparation that diuron 400g/L makes as active component
Prepare said preparation as follows:
In the beaker of appropriate size, add about 150g/LD130, the most the desired amount of2510、12A3N and3665.Then by this mixture mild heat (about
30-40 DEG C) a few minutes, then expose under high shear mixing to form uniform predispersion.Once it is cooled to ambient temperature, point
Dissipate and the desired amount of do not grind diuron (95%w/w technology) and continue high shear mixing a few minutes.Then make said preparation settle, use
AddD130(is if necessary) make volume required and again shear until uniformly.
Said preparation initially presents the most low viscous flat-white dispersion, and it is easy when diluting in 20ppm Environmental Water
Emulsifying.Notice generation syneresis within a few minutes.After storing 14 days at 54 DEG C, it was observed that above-mentioned preparation has occurred 55%
Syneresis and exist can thoroughly but the hardest gel-like matrix, its stirring time verified being difficult to fluidize.
Said preparation shows the relatively poor stability provided owing to lacking suitable rheology modifier.
Embodiment 27(contrast)
Use the OD preparation that G-30027 400g/L makes as active component
Method according to outlining in embodiment 26 prepares said preparation:
Said preparation initially presents the most moderately viscous flat-white dispersion, and it produces properly in 20ppm Environmental Water
Emulsifiability.After storing 14 days at 54 DEG C, said preparation shows 48% syneresis, and major part is by uniform gel the most thoroughly
Shape structure is constituted, and it can revert to store flowable denseness as front outer appearnce with it by stirring.
Use rubber-type copolymer (
G-1701 prepolymer) OD preparation is directly prepared as antisettling agent
Embodiment 28
G-1701 polymer is described as the diblock polymer of styrene and polyethylene/polypropylene.
Lower series preparation is prepared in mode similar in the way of for embodiment 24；But, mix in high shear before the milling
Close lower additionG-1701 polymer and enuatrol:
Being stored at 54 DEG C 2 weeks by said preparation, hereafter it shows significantly improving of viscosity, but does not has strong flocbed
Sign.
This preparation provides certain storage stability to improve.But, emulsification property when diluting in water is poor.
Use the embodiment of the structural agent premix composition comprising oil & fat hydrochlorate
Embodiment 29
The preparation of structuring agent premix:
Prepare premix composition as follows:
Required oily total amount is heated to 80 DEG C-90 DEG C.WillG-1701 polymer adds in deep fat and makes
Produce limpid without gel/particle liquid by effective stirring and dissolving.
Then enuatrol is dispersed inIn G-1701 polymer/oil mixture.This mixture is in stirring
While be maintained at 80 DEG C-90 DEG C until appearance uniform, hereafter make this mixture be cooled to 60 DEG C.
When this oil mixture reaches 60 DEG C, addDispersant is also fully dissolved by 2510 dispersants
In this oil mixture.
Once making, this mixture can use or be cooled to ambient temperature storage in case using after a while at 60 DEG C.
This mixture still quite stable and flowable when storing.
Embodiment 30
Comprise the preparation of Mancozeb (480g/L) preparation of OD premix composition
Prepare said preparation as follows:
The oily blend made in embodiment 29 together with the 90% of required remaining oil adds
2510 dispersants.Tod by high shear mixingAfter 2510 dispersants dissolve most 15 minutes in this oil
Under continuing high shear mixing, Mancozeb (85%w/w technology) is added in this oil blend immediately.By pre-for this Mancozeb
Mixed thing is transferred in ball mill and continues to grind until obtaining the particle mean size (d less than 5 microns (μm)0.5).
Then emulsifying agent is the most disposably added in the pre-composition of grinding, complete to guarantee each emulsifying agent
Full homogenizing.
Then with otherFinal preparation is joined full volume by D130.
Being stored at 54 DEG C by said preparation 2 weeks, hereafter it only shows the slight raising of viscosity, does not has strong flocbed
Sign, and syneresis slight (< 1%).Emulsion characteristic improvement compared with embodiment before when diluting in water, but still
Less than optimal.
Embodiment 31
Comprise the preparation of Mancozeb (567g/L) preparation of OD premix composition
The lower series preparation of method preparation according to described in embodiment 30:
Said preparation is stored 2 weeks at 54 DEG C.Said preparation shows the storage stability of excellence, does not has formulation viscosity to improve
Or hard layer and (< 1%) syneresis.Emulsion characteristic when diluting in water greatly improves.This preparation at 54 DEG C 6 weeks
After still show good flowability.
Embodiment 32
Comprising of fat-free hydrochlorateThe pre-composition of D-130
Prepare having structure agent:
G-1701 polymer 4%w/w
2510 dispersants 2.5
D130 93.5
Required oily total amount is heated to 80 DEG C-90 DEG C.WillG-1701 polymer adds in deep fat and makes
Produce limpid without gel/particle liquid by effective stirring and dissolving.
This mixture stirring while be maintained at 80 DEG C-90 DEG C until appearance uniform, hereafter make this mixture be cooled to
60℃。
When this oil mixture reaches 60 DEG C, addDispersant is also fully dissolved by 2510 dispersants
In this oil mixture.
Once making, this mixture can use or be cooled to ambient temperature storage in case using after a while at 60 DEG C.
This mixture still quite stable and flowable when storing.
Embodiment 33
Use the preparation that the pre-composition of embodiment 32 is made
According to series preparation under the method manufacture described in embodiment 30:
After storing 2 weeks at 54 DEG C, said preparation shows the slight raising of viscosity, does not has hard layer or flocculation sign.?
Emulsion characteristic when diluting in water is similar to embodiment 30.
Embodiment 34
Preparation comprisesThe following pre-composition of 150:
G-1701 18.18%w/w
150 81.88
Add the desired amount of in appropriate containers150 HesG-1701.Gained mixture with
After under mild agitation heating until observing gel but still the degree of flowable homogeneous consistency.When cooling, viscosity is entered
One step improves can process gel to be formed, and is stored in case using after a while.
Embodiment 35
Prepare following OD preparation:
In the beaker of appropriate size, add about 150g/L EXXSOL D130, remaining inertia group the most the desired amount of
Point.Then this mixture is imposed medium paramount heating (about 50-60 DEG C) until structural agent is incorporated to, then cause high shear
Mixing is to form uniform predispersion.Once it is cooled to ambient temperature, disperses the desired amount of not grind diuron (95%w/w skill
Art) and continue high shear mixing 5 minutes.Then said preparation is made to settle, with addD130(is if necessary) make
Volume required and again shear 10 minutes to guarantee uniformly.
Said preparation initially presents the most moderately viscous flat-white dispersion.When dilution in 20ppm Environmental Water,
The residue suspendability of 78.0% is observed after 30 minutes.After storing 7 days under ambient lab temperature, it was observed that 45% dehydration is received
Contracting, and most of suspension of remaining sedimentation shows as gel-type vehicle the most thoroughly, it is reversible to produce uniform fluid via stirring
Dispersion.
Said preparation shows, although being initially observed rheology modified, but is produced by the existence of traditional oils emulsifying agent and arsol
Raw antagonism.
The embodiment of OF preparation, i.e. emulsifier-free
Embodiment 36
Prepare following OF preparation:
By under shear-mixed, diuron activating agent is added to oil andWith system in 2510 dispersants
Make 58%w/w pre-composition, prepare preparation.Then this pre-composition is ground to the particle mean size less than 2 microns to produce grinding
Material.The addition of structurant of embodiment 3 is added under high shear mixing in this abrasive.
Said preparation is stored at 54 DEG C and 20 DEG C, does not the most observe hard layer.Said preparation only also shows
20% syneresis, this is to significantly improve compared with the embodiment of non-structure agent.
Embodiment 37
Following OF preparation is prepared according to the method for general introduction in embodiment 35:
Said preparation initially presents the most low viscous flat-white dispersion.When dilution in 20ppm Environmental Water, due to
Lack suitable emulsifying agent, it was observed that the suspendability of difference.After storing 6 days under ambient lab temperature, said preparation is the most equal
Even flowable, there is 7.5% syneresis.At 54 DEG C after the phase same time, although said preparation is flowable, but show 56.1%
Syneresis.
At ambient conditions, said preparation changes expected from showing compared with embodiment 35 owing to getting rid of traditional oils emulsifying agent
Enter performance.
Embodiment 38
Method according to outlining in embodiment 35 prepares following OF preparation, it is noted that in this case, only addsG-1701 is to produce the utilization rate improved:
Said preparation initially presents the flat-white dispersion of viscosity in relatively low at.When dilution in 20ppm Environmental Water,
Owing to lacking suitable emulsifying agent, it was observed that the suspendability of difference.After storing 6 days under ambient lab temperature, said preparation is still
Flowable, it was observed that trace syneresis.At 54 DEG C after the phase same time, major part preparation is the most flowable, it was observed that 55.0% takes off
Water shrinks.
Relevant to the emulsifying agent getting rid of antagonism and arsol, said preparation shows the stability of improvement.
The embodiment using rubber-type copolymer of FAF
Embodiment 39
Prepare following OD preparation:
By manufacturing 58%w/w abrasive as described in example 36 above, prepare said preparation.Grind to this under high shear mixing
In abrasive material add embodiment 32 addition of structurant and3665 emulsifying agents.
Said preparation is stored at 54 DEG C and 20 DEG C, does not the most observe hard layer.Said preparation shows 32% and takes off
Water shrinks, and this is still compared with the embodiment of non-structure agent and significantly improves.
It is contemplated that optimize the content of addition of structurant and dispersant further so that this preparation realizes acceptable de-
Water shrinks level.
Embodiment 40
Method according to outlining in embodiment 35 prepares following OD preparation, but in this case it should be noted that only addG-1701 is to produce the utilization rate improved:
Said preparation initially presents the most full-bodied flat-white dispersion.When dilution in 20ppm Environmental Water, 30
The residue suspendability of 76.2% is observed after minute.After storing 14 days at 54 DEG C, it was observed that 41.7% syneresis, and remaining
Most of suspension thickening of sedimentation becomes the most flowable state, and it is reversible to produce uniform fluid dispersion via stirring
Body.Under ambient lab temperature after the phase same time, said preparation shows identical characteristics, but records 32.1% syneresis.
Said preparation shows, although initially high viscosity, but improveThe utilization rate of G-1701 the most fully overcomes
Use the antagonism that typical emulsifier provides.
Embodiment 41
Method according to outlining in embodiment 35 prepares following OD preparation, but initially only adds 50g/L
D130:
Structured blend used in embodiment 29,
CompriseG-1701、
2510, enuatrol and
D130 180.00
D130 joins full volume (1 liter)
Said preparation initially presents the flat-white dispersion of viscosity in relatively low at, when it dilutes in 20ppm Environmental Water
Easily emulsifying.After storing 14 days at 54 DEG C, producing 44% syneresis, major part is made up of uniform gel-like structure the most thoroughly,
It can partly revert to flowable denseness by stirring.At ambient temperature after 14 days, said preparation is the most flowable and shows 28%
Syneresis.
This preparation by withG-1701 is used in combination enuatrol and shows the stability of improvement, thus presses down
The formation of syneresis processed.In this sample and stored at ambient temperature after initial preparation the most particularly significant.
Embodiment 42
Preparation comprise more soap andThe following premix composition of 150 solvents:
Add the desired amount of in appropriate containers150、D130 andG-
1701.Gained mixture is heated to 60 DEG C the most under mild agitation until observing thickness but the degree of homogeneous consistency.Then
Add enuatrol and continue the stirring opaque flowable gel of formation.Cooling time, viscosity improve further with formed can add
Work gel, is stored in case using after a while.
Embodiment 43
Method according to outlining in embodiment 35 prepares following OD preparation:
From the structured blend of embodiment 42,
CompriseG-1701, enuatrol,
150 HesD130 60.00
D130 joins full volume (1 liter)
Said preparation initially presents the flat-white dispersion of viscosity in relatively low at.In 20ppm Environmental Water during dilution, should
Preparation produces the residue suspendability of 61.0% after 30 minutes.After storing 7 days at 54 DEG C, said preparation shows 31.7% dehydration
Shrink, and major part is the most flowable, despite some thickening effects.At ambient temperature after 7 days, said preparation is the most flowable and equal
Even, record 7.9% syneresis.
This preparation all shows the syneresis of improvement under environment and 54 DEG C of conditions of storage, particularly the former.
Embodiment 44
Method according to outlining in embodiment 35 prepares following OD preparation:
From the structured blend of embodiment 42,
CompriseG-1701, enuatrol,
150 HesD130 60.00
D130 joins full volume (1 liter)
Said preparation initially presents the most moderately viscous flat-white dispersion.In 20ppm Environmental Water during dilution, this system
The easy emulsifying of agent is with the residue suspendability producing 76.7% after 30 minutes.After storing 5 days at 54 DEG C, said preparation shows
Only 13.8% syneresis, major part suspension is the most flowable.At ambient temperature after the phase same time, said preparation is the most flowable, only
Show trace syneresis.
Said preparation shows and comprisesG-1701, enuatrol,150 Hes
The structured blend from embodiment 42 of D130 is used together raisingThe improvement of 2510 content
Effect.
Embodiment 45
According to the lower series preparation of the method preparation outline in embodiment 35, but in this case, use is referred to asAnother polyamine-fatty acid condensates of 4890 is as main dispersant:
From the structured blend of embodiment 42,
CompriseG-1701, enuatrol,
150 HesD130 60.00
D130 joins full volume (1 liter)
Said preparation initially presents the most moderately viscous flat-white dispersion.In 20ppm Environmental Water during dilution, this system
The easy emulsifying of agent is with the residue suspendability producing 71% after 30 minutes.After storing 2 days at 54 DEG C, said preparation shows
30.8% syneresis, major part is made up of uniform gel-like structure the most thoroughly, outside it passes through before stirring can revert to store with it
See similar flowable denseness.At ambient temperature after 7 days, said preparation is the most flowable, shows only 6.8% syneresis.
Said preparation shows to compriseG-1701, enuatrol,150 HesD130
The structured blend from embodiment 42 still provide static stabilization when being used together with another dispersant.
Embodiment 46
According to the lower series preparation of the method preparation outline in embodiment 35:
From the structured blend of embodiment 34,
CompriseG-1701 and
150 20.00
D130 joins full volume (1 liter)
Said preparation initially presents the most moderately viscous flat-white dispersion, and it provides suitable in 20ppm Environmental Water
Emulsifiability.After storing 14 days at 54 DEG C, said preparation shows 25% syneresis, and major part is by uniform gel the most thoroughly
Shape structure is constituted, and it can revert to store flowable denseness as front outer appearnce with it by stirring.
This formulations display goes out significantly improving of stability, particularly in terms of syneresis.This is attributable to use in fact
Executing the structured blend outline in example 34, it comprisesG-1701 and150。
The display high build Pluronic PE 6800 embodiment to the effect of rubber-type copolymer
Embodiment 47
The lower series preparation of preparation:
From the structured blend of embodiment 34,
CompriseG-1701 and
150 20.00
G250H joins full volume (1 liter)
In the beaker of appropriate size, add 359.12g/LG250H, the most the desired amount of2510、DS10595、3665 HesPE103.Then this mixture gentleness is added
Heat (about 30-40 DEG C) a few minutes, then expose under high shear mixing to form uniform predispersion.Once it is cooled to environment
Temperature, disperses the desired amount of Mancozeb (85%w/w technology), then gradually adds comprising from embodiment 34G-1701 andThe structured blend of 200.Then gained mixture is imposed further height
Shear until obtaining uniform without agglomerate dispersion.In this case it should be noted that use the poly-alkylene two being referred to as DS10595
Alcohol ether fatty acid condensates blend is as secondary dispersant.
Said preparation initially presents moderately viscous homogeneous yellow dispersion.At 30 DEG C in 342ppm hard water during dilution,
Said preparation produces the residue suspendability of 88.1% after 30 minutes.
After storing 14 days at 54 DEG C, in addition to viscosity slightly improves, still part is flowable and shows 6.9% dehydration for said preparation
Shrinking, this is owing to the gel-type vehicle that there is weak structure.There is also the soft accumulation horizon (packing) of pettiness, in gentle agitation
Lower easily reverse.
When using term " to comprise " in this manual, they should be interpreted to specify the described feature, whole being previously mentioned
Number, step or the existence of component, but do not preclude the presence or addition of one or more further feature, integer, step, component or its group
Close.
Claims (30)
1. being used in the premix composition in agricultural Oil-based Suspension preparation, what wherein said compositions was included in oil contains at least benzene
Ethylene optionally comprises selected from butadiene, second as the unsaturated rubber type copolymer of residue, described unsaturated rubber type copolymer
Another olefin hydrocarbon molecules of one or more in alkene, propylene, isoprene and butylene,
Wherein said agricultural Oil-based Suspension preparation comprises the active component being suspended in finely divided form in oil；Above-mentioned with at least one
Unsaturated rubber type copolymer or its mixture, wherein said preparation does not contains organophilic clay,
And wherein said compositions comprises at least one C further8-C20Organic acid or its salt or its mixture.
Premix composition the most according to claim 1, wherein said organic salt comprises C10-C18Carbochain, wherein salt forming anion choosing
From carboxylate radical, sulfate radical, sulfonate radical, phosphate radical or phosphonium acid ion；And wherein salt-forming cation selected from sodium, calcium, magnesium, potassium, aluminum,
Ammonium, alkylammonium or alkanol ammonium and other common monovalence, bivalence and trivalent ion.
Premix composition the most according to claim 2, wherein said organic salt comprises sodium lauryl sulphate.
Premix composition the most according to claim 2, wherein said acylate is selected from the salt of fatty acid；Substituted or unsubstituted
Straight or branched alkyl or the salt of alkenyl；With replacement or the salt of unsubstituting aromatic yl.
Premix composition the most according to claim 4, the fatty acid of wherein said soap is selected from oleic acid, stearic acid, lima bean
Cool acid, Palmic acid, lauric acid and multi-hydroxy stearic acid and wherein salt-forming cation are selected from sodium, calcium, magnesium, potassium, aluminum, ammonium, alkylammonium
Or alkanol ammonium and other common monovalence, bivalence and trivalent ion.
Premix composition the most according to claim 5, wherein said soap selected from enuatrol, potassium oleate, sodium stearate, two
Calcium oleate, distearyl acid calcium and multi-hydroxy stearic acid calcium.
Premix composition the most according to claim 2, wherein said acylate comprises containing C12-C16The alkenyl of carbochain
Salt, and the salt forming anion of wherein said organic acid is selected from sulfate radical, sulfonate radical, phosphate radical or phosphonium acid ion.
Premix composition the most according to claim 2, wherein said acylate comprises containing C10-C16The alkylaryl of carbochain
Salt；And the salt forming anion of wherein said organic acid is selected from sulfate radical, sulfonate radical, phosphate radical or phosphonium acid ion.
Premix composition the most according to claim 8, wherein said acylate is linear alkylbenzene sulfonate (LAS).
Premix composition the most according to claim 1, comprises further be applicable to the table being dispersed in oil by hydrophobic solid medium
Face activating agent dispersant.
11. premix compositions according to claim 10, wherein said surfactant-dispersed agent comprises at least one poly-alkylene
Glycol-fatty acid condensates, the molecular weight of wherein said alkylene glycol part is more than 1500amu.
12. premix compositions according to claim 1, wherein said copolymer is selected from SB, benzene second
Alkene-polyethylene/polypropylene or styrene-isoprene copolymer.
13. according to the premix composition of claim 1 or claim 2, wherein said preparation comprise further selected from butadiene,
Another olefin hydrocarbon molecules of ethylene, propylene, isoprene or butylene or its mixture.
14. premix compositions according to claim 1, wherein said preparation is selected from oil dispersible preparation " OD " or can miscible flow by oil
Dynamic " OF " preparation.
15. premix compositions according to claim 14, wherein said preparation is OD preparation.
16. premix compositions according to claim 15, comprise at least one alkyl alcoxyl with the HLB higher than 10 further
Base compound.
17. premix compositions according to claim 15, comprise further at least one single block with the HLB higher than 10 or
Diblock Pluronic PE 6800.
18. premix compositions according to claim 15, comprise emulsifying agent further.
19. premix compositions according to claim 18, wherein said emulsifier package contains at least one ployalkylene glycol-fatty acid
Condensation substance, the molecular weight of wherein said alkylene glycol part is more than 1500amu.
20. premix compositions according to claim 1, wherein said active component is selected from Mancozeb, diuron, G-30027
Or captan.
21. premix compositions according to claim 20, wherein said active component is Mancozeb.
22. premix compositions according to claim 20, wherein Mancozeb exists with the concentration more than 400g/L.
23. preparations, according to the method for the premix composition of any one of claim 1-22, wherein heat described rubber-type in oil
Copolymer is until producing clear fluid.
24. use the method that premix composition according to claim 1 prepares Oil-based Suspension preparation.
25. methods according to claim 24, farther include to add at least one emulsifying agent or surfactant-dispersed agent with
Manufacture the step of OD preparation.
26. methods according to claim 25, the active component in wherein said preparation is selected from Mancozeb, diuron, Aunar
Draw Tianjin or captan.
27. methods according to claim 26, at least one emulsifying agent wherein said is selected from the dialkyl sulfosuccinate fourth of anhydrous form
Diacid salt, alcohol ethoxylate, sorbitan ester and sorbitan ester ethoxylate, ethoxylated fatty acid, ethoxy
Base Oleum Ricini and ethoxylated alkylamine or its mixture.
28. preparations comprise the method for the OD preparation of active component, including step:
A) preparation is according to the premix composition of any one of claim 1-22；
B) not with or together with oily and the most other other dispersant, active component is dispersed in described premix composition；
C) active component dispersion is ground to realize the particle mean size of 1-12 micron；
D) it is optionally added to a kind of other organic acid or its salt；
E) surfactant emulsifiers is added；With
F) optionally through the additional oily final content of active component that regulates to realize continuous phase,
Wherein step a) is to e) carrying out in any order.
29. methods according to claim 28, wherein step (f) includes adding at least one ployalkylene glycol-fatty acid condensation
Thing, the molecular weight of wherein said alkylene glycol part is more than 1500amu.
30. methods according to claim 28, wherein said active component selected from Mancozeb, diuron, G-30027 and gram
Bacterium is red.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610805511.XA CN106417272B (en) | 2011-06-10 | 2012-06-08 | Agricultural oil-based suspension formulation |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2011902298A AU2011902298A0 (en) | 2011-06-10 | Composition and method for enhancing the physical stability of agricultural oil-based suspension formulations | |
| AU2011902298 | 2011-06-10 | ||
| PCT/AU2012/000661 WO2012167321A1 (en) | 2011-06-10 | 2012-06-08 | Composition and method for enhancing the physical stability of agricultural oil-based suspension formulations |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610805511.XA Division CN106417272B (en) | 2011-06-10 | 2012-06-08 | Agricultural oil-based suspension formulation |
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| Publication Number | Publication Date |
|---|---|
| CN103501596A CN103501596A (en) | 2014-01-08 |
| CN103501596B true CN103501596B (en) | 2016-10-05 |
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| CN201280020206.XA Expired - Fee Related CN103501596B (en) | 2011-06-10 | 2012-06-08 | For improving compositions and the method for the physical stability of agricultural Oil-based Suspension preparation |
| CN201610805511.XA Expired - Fee Related CN106417272B (en) | 2011-06-10 | 2012-06-08 | Agricultural oil-based suspension formulation |
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| CN201610805511.XA Expired - Fee Related CN106417272B (en) | 2011-06-10 | 2012-06-08 | Agricultural oil-based suspension formulation |
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| US (2) | US20150099635A1 (en) |
| EP (1) | EP2717682B1 (en) |
| JP (2) | JP2014516055A (en) |
| KR (1) | KR101942238B1 (en) |
| CN (2) | CN103501596B (en) |
| AR (1) | AR086882A1 (en) |
| AU (1) | AU2012267212B2 (en) |
| BR (1) | BR112013026574A8 (en) |
| CA (1) | CA2833406C (en) |
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| WO (1) | WO2012167321A1 (en) |
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| BR102013009504A2 (en) * | 2013-04-18 | 2015-03-17 | Oxiteno S A Indústria E Comércio | Oil dispersion type agrochemical formulation, use of oil dispersion type agrochemical formulations and process for obtaining oil dispersion type agrochemical formulation |
| GB201320627D0 (en) | 2013-11-22 | 2014-01-08 | Croda Int Plc | Agrochemical concentrates |
| US10793768B2 (en) | 2016-04-29 | 2020-10-06 | PfP Industries LLC | Polyacrylamide slurry for fracturing fluids |
| BR102017010745A2 (en) | 2016-05-24 | 2018-02-27 | Adama Makhteshim Ltd. | FUNGICIDE OIL FORMULATION, FUNGICIDE SUSPOEMULSION AND USE OF FUNGICIDE OIL FORMULATION |
| US20200305419A1 (en) * | 2016-11-18 | 2020-10-01 | Indorama Ventures Oxides Australia Pty Limited | Co-Formulation Comprising a Plant Growth Regulator and an Oil, and Methods of Preparing and Using Said Co-Formulation |
| KR101887617B1 (en) * | 2017-09-19 | 2018-09-10 | 주식회사 태현 | flame resisting thread manufacturing method, and net safety using flame resisting thread |
| JP7249341B2 (en) * | 2017-11-30 | 2023-03-30 | ダウ グローバル テクノロジーズ エルエルシー | Hydrophobic polymers as oil rheology modifiers for agrochemical formulations |
| CN109730061B (en) * | 2018-12-27 | 2021-12-28 | 广西田园生化股份有限公司 | Stabilizer of pesticide granules and application thereof |
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- 2012-06-08 MX MX2013012364A patent/MX365623B/en active IP Right Grant
- 2012-06-08 WO PCT/AU2012/000661 patent/WO2012167321A1/en active Application Filing
- 2012-06-08 JP JP2014513862A patent/JP2014516055A/en active Pending
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- 2012-06-08 ES ES12796683T patent/ES2758402T3/en active Active
- 2012-06-08 BR BR112013026574A patent/BR112013026574A8/en not_active IP Right Cessation
- 2012-06-08 CN CN201610805511.XA patent/CN106417272B/en not_active Expired - Fee Related
- 2012-06-08 AU AU2012267212A patent/AU2012267212B2/en not_active Ceased
- 2012-06-08 EP EP12796683.6A patent/EP2717682B1/en active Active
- 2012-06-08 CA CA2833406A patent/CA2833406C/en not_active Expired - Fee Related
- 2012-06-08 AR ARP120102047A patent/AR086882A1/en active IP Right Grant
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- 2013-10-08 ZA ZA2013/07518A patent/ZA201307518B/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101942238B1 (en) | 2019-01-25 |
| JP6259506B2 (en) | 2018-01-10 |
| MX365623B (en) | 2019-06-10 |
| EP2717682A1 (en) | 2014-04-16 |
| US20150099635A1 (en) | 2015-04-09 |
| BR112013026574A8 (en) | 2018-01-23 |
| AU2012267212B2 (en) | 2015-07-30 |
| CA2833406A1 (en) | 2012-12-13 |
| JP2017039769A (en) | 2017-02-23 |
| WO2012167321A8 (en) | 2013-10-31 |
| AU2012267212A1 (en) | 2013-10-24 |
| CN106417272B (en) | 2020-03-31 |
| AR086882A1 (en) | 2014-01-29 |
| ZA201307518B (en) | 2015-04-29 |
| EP2717682B1 (en) | 2019-09-04 |
| WO2012167321A1 (en) | 2012-12-13 |
| EP2717682A4 (en) | 2014-11-26 |
| MX2013012364A (en) | 2014-04-14 |
| US20190357528A1 (en) | 2019-11-28 |
| CN106417272A (en) | 2017-02-22 |
| CA2833406C (en) | 2019-07-30 |
| BR112013026574A2 (en) | 2017-07-18 |
| ES2758402T3 (en) | 2020-05-05 |
| CN103501596A (en) | 2014-01-08 |
| JP2014516055A (en) | 2014-07-07 |
| KR20140032389A (en) | 2014-03-14 |
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